U.S. patent application number 14/498231 was filed with the patent office on 2015-01-15 for surfactants and solvents containing diels-alder adducts.
The applicant listed for this patent is Stepan Company. Invention is credited to Randal J. Bernhardt, Franz J. Luxem, Rick Tabor, Gregory James Wallace, Chunhua Yao.
Application Number | 20150018563 14/498231 |
Document ID | / |
Family ID | 49261208 |
Filed Date | 2015-01-15 |
United States Patent
Application |
20150018563 |
Kind Code |
A1 |
Tabor; Rick ; et
al. |
January 15, 2015 |
Surfactants and Solvents Containing Diels-Alder Adducts
Abstract
Surfactants and solvents containing derivatized adducts formed
from Diels-Alder reactions of terpenes and unsaturated carboxylic
acids or their derivatives are disclosed. Processes for making and
derivatizing the Diels-Alder adducts are also disclosed.
Inventors: |
Tabor; Rick; (Plymouth,
MI) ; Bernhardt; Randal J.; (Antioch, IL) ;
Luxem; Franz J.; (Palatine, IL) ; Yao; Chunhua;
(Carmel, IN) ; Wallace; Gregory James; (Chicago,
IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Stepan Company |
Northfield |
IL |
US |
|
|
Family ID: |
49261208 |
Appl. No.: |
14/498231 |
Filed: |
September 26, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/US2013/034113 |
Mar 27, 2013 |
|
|
|
14498231 |
|
|
|
|
61615949 |
Mar 27, 2012 |
|
|
|
Current U.S.
Class: |
548/478 ;
558/32 |
Current CPC
Class: |
C11D 1/26 20130101; A61K
8/463 20130101; C11D 1/74 20130101; A01N 25/30 20130101; A61K 8/362
20130101; C11D 1/143 20130101; C07C 303/04 20130101; A61Q 5/12
20130101; C07C 2601/16 20170501; C11D 1/28 20130101; C07D 209/48
20130101; C11D 1/75 20130101; A61K 8/31 20130101; C07C 305/16
20130101; A61K 8/39 20130101 |
Class at
Publication: |
548/478 ;
558/32 |
International
Class: |
C07D 209/48 20060101
C07D209/48; C07C 303/04 20060101 C07C303/04; C07C 305/16 20060101
C07C305/16 |
Claims
1. A composition comprising a cationic, amine oxide, amphoteric,
anionic, or nonionic surfactant which is the reaction product of
(i) a Diels Alder adduct formed from: (a) farnesene or myrcene or
mixtures thereof; and (b) a dienophile selected from the group
consisting of maleic anhydride, itaconic anhydride, dimethyl
maleate, dimethyl itaconate, maleic acid, itaconic acid, fumaric
acid, dimethyl fumarate, acrylic acid, methyl acrylate, ethyl
acrylate, butyl acrylate, methyl methacrylate, methacrylic acid,
benzaldehyde, hydroxyethyl acrylate, hydroxyethyl methacrylate,
hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylonitrile,
acrylamide, N-hydroxyethyl maleimide, maleimide, vinyl alkyl
ketones, methacrolein, and mixtures thereof; reacted with (ii) at
least one derivatizing agent selected from the group consisting of:
mono-alkyl ether of polyethylene glycol, mono-alkyl ether of
polypropyloxy-polyethyloxy block copolymer, mono-alkyl ethers of
polybutyloxy-polyethyloxy block copolymer, amine-containing
alkylene glycol, amine-containing polyalkylene glycol, mono- or
oligo-alkylene glycol, amine, polyamine, aliphatic alcohol,
cycloaliphatic sultone, aromatic substituted alcohol, hydrogenating
agent, aryloxy alkylene alcohol, sulfonating agent, phosphating
agent, sulfating agent, aryl-alkyl halide, dimethyl sulfate,
epichlorohydrin, and combinations thereof.
2. The composition of claim 1, wherein the dienophile is maleic
anhydride, itaconic anhydride, dimethyl maleate, dimethyl
itaconate, maleic acid, itaconic acid, fumaric acid, dimethyl
fumarate, acrylic acid, methyl acrylate, ethyl acrylate, butyl
acrylate, methyl methacrylate, methacrylic acid, or mixtures
thereof, and the at least one derivatizing agent is selected from
mono-alkyl ether of polyethylene glycol, mono-alkyl ether of
polypropyloxy-polyethyloxy block copolymer, mono-alkyl ether of
polybutyloxy-polyethyloxy block copolymer, and mixtures thereof,
wherein the derivatizing agent comprises from one to about 30 moles
of ethylene oxide and the alkyl ether group contains from 1 to 6
carbons.
3. The composition of claim 1, wherein the dienophile is maleic
anhydride, itaconic anhydride, dimethyl maleate, dimethyl
itaconate, maleic acid, itaconic acid, fumaric acid, dimethyl
fumarate, acrylic acid, methacrylic acid, methyl acrylate, methyl
methacrylate, or mixtures thereof, and the at least one
derivatizing agent comprises the combination of at least one
aromatic alcohol, a hydrogenating agent, and at least one
sulfonating agent.
4. The composition of claim 3, wherein the aromatic alcohol is an
aromatic substituted hydroxy alkane.
5. The composition of claim 4, wherein the sulfonating agent is
sulfur trioxide or a derivative thereof.
6. The composition of claim 1, wherein the dienophile is
acrylonitrile, and the derivatizing agent comprises the combination
of at least one hydrogenating agent, at least one aliphatic
alcohol, and at least one alkyl halide, aryl alkyl halide,
epichlorohydrin, or dimethyl sulfate.
7. The composition of claim 6, wherein the at least one
hydrogenating agent is hydrogen.
8. The composition of claim 6, wherein the at least one aliphatic
alcohol is methanol.
9. The composition of claim 6, wherein the at least one alkyl
halide is methyl chloride.
10. The composition of claim 6, wherein the at least one aryl alkyl
halide is benzyl chloride.
11. A composition comprising a solvent which is the reaction
product of (i) a Diels Alder adduct formed from: (a) farnesene,
myrcene or mixtures thereof; and (b) a dienophile selected from the
group consisting of maleic anhydride, itaconic anhydride, dimethyl
maleate, dimethyl itaconate, maleic acid, itaconic acid, fumaric
acid, dimethyl fumarate, acrylic acid, methyl acrylate, ethyl
acrylate, butyl acrylate, methyl methacrylate, methacrylic acid,
and mixtures thereof; reacted with (ii) at least one derivatizing
agent selected from the group consisting of monoalkyl ethers of
polyethylene glycols, mono-alkyl ethers of
polypropyloxy-polyethyloxy block copolymers, mono-alkyl ethers of
polybutyloxy-polyethyloxy block copolymers, aliphatic alcohols,
aromatic alcohols, aryloxy alkylene alcohols, hydrogenating agents,
alkyl halides, aryl-alkylhalides, and combinations thereof.
12. The composition of claim 11, wherein the dienophile is maleic
anhydride, itaconic anhydride, dimethyl maleate, dimethyl
itaconate, maleic acid, itaconic acid, fumaric acid, dimethyl
fumarate, acrylic acid, methacrylic acid, methyl acrylate, ethyl
acrylate, butyl acrylate, methyl methacrylate, or mixtures thereof,
and the at least one derivatizing agent is selected from monoalkyl
polyethylene glycol, mono-alkyl ethers of
polypropyloxy-polyethyloxy block copolymers, mono-alkyl ethers of
polybutyloxy-polyethyloxy block copolymers, and mixtures
thereof.
13. The composition of claim 11, wherein the dienophile is maleic
anhydride, itaconic anhydride, dimethyl maleate, dimethyl
itaconate, maleic acid, itaconic acid, fumaric acid, dimethyl
fumarate, acrylic acid, methacrylic acid, methyl acrylate, ethyl
acrylate, butyl acrylate, methyl methacrylate, or mixtures thereof,
and the at least one derivatizing agent is at least one aromatic or
aryloxy alkylene alcohol.
14. The composition of claim 11, wherein the aromatic or aryloxy
alkylene alcohol is an aromatic substituted hydroxy alkane.
15. A process for producing a surfactant or solvent derived from a
Diels-Alder adduct, comprising the steps of: (a) forming a
Diels-Alder adduct by reacting farnesene, myrcene, or mixtures
thereof with at least one dienophile selected from the group
consisting of maleic anhydride, itaconic anhydride, dimethyl
maleate, dimethyl itaconate, maleic acid, itaconic acid, fumaric
acid, dimethyl fumarate, acrylic acid, methacrylic acid, methyl
acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
acrylonitrile, acrylamide, and mixtures thereof; and (b) reacting
the Diels-Alder adduct with at least one derivatizing agent
selected from the group consisting of: mono-alkyl ether of
polyethylene glycol, mono-alkyl ether of polypropyloxy-polyethyloxy
block copolymer, mono-alkyl ethers of polybutyloxy-polyethyloxy
block copolymer, mono- or oligo-alkylene glycol, amine, polyamine,
aliphatic alcohol, cycloaliphatic sultone, aromatic substituted
alcohol, hydrogenating agent, aryloxy alkylene alcohol, sulfonating
agent, phosphating agent, sulfating agent, alkyl halide, aryl-alkyl
halide, dimethyl sulfate, epichlorohydrin, and combinations
thereof.
16. The process of claim 15, wherein the Diels-Alder adduct is
reacted with monoalkyl polyethylene glycol, mono-alkyl ether of
polypropyloxy-polyethyloxy block copolymer, mono-alkyl ether of
polybutyloxy-polyethyloxy block copolymer, or mixtures thereof to
form an ester of the Diels-Alder adduct.
17. The process of claim 15, wherein the Diels-Alder adduct is
reacted with monoalkyl polyethylene glycol, mono-alkyl ether of
polypropyloxy-polyethyloxy block copolymer, mono-alkyl ether of
polybutyloxy-polyethyloxy block copolymer, or mixtures thereof in
equimolar amounts, and the reaction product is further reacted with
a base.
18. The process of claim 15, wherein the Diels-Alder adduct is
reacted with at least one aromatic or aryloxy alkylene alcohol to
form an intermediate ester reaction product, and the intermediate
ester reaction product is further reacted with a hydrogenating
agent and at least one sulfonating agent.
19. The process of claim 18, wherein the at least one aromatic or
aryloxy alkylene alcohol is 2-phenoxyethanol, benzyl alcohol,
2-phenyl ethanol, an ethoxylated phenol, or a mixture thereof.
20. The process of claim 15, wherein the Diels-Alder adduct is
formed from farnesene, myrcene, or mixtures thereof and
acrylonitrile, and the adduct is reacted with at least one
hydrogenating agent, and further reacted with at least one
aliphatic alcohol and at least one alkyl or aryl halide or
epichlorohydrin or dimethyl sulfate or a mixture thereof.
21. The process of claim 20, wherein the hydrogenating agent is
hydrogen gas.
22. The process of claim 20, wherein the at least one aliphatic
alcohol is methanol.
23. The process of claim 20, wherein the at least one alkyl halide
is methyl chloride.
24. The process of claim 20, wherein the at least one aryl halide
is benzyl chloride.
25. A composition comprising a nonionic surfactant which is the
reaction product of a Diels Alder adduct formed from: (a) farnesene
or myrcene or mixtures thereof; and (b) a dienophile containing a
monoalkyl ether of polyethylene glycol, a monoalkyl ether of a
polypropyloxy-polyethyloxy block copolymer, or a polyalkylene
glycol containing ethylene oxide, propylene oxide, butylene oxide,
or mixtures thereof.
26. A process for producing a surfactant derived from a Diels-Alder
adduct comprising the steps of: (i) derivatizing (a) a dienophile
selected from the group consisting of maleic anhydride, itaconic
anhydride, dimethyl maleate, dimethyl itaconate, maleic acid,
itaconic acid, fumaric acid, dimethyl fumarate, acrylic acid,
methyl acrylate, ethyl acrylate, methyl methacrylate, methacrylic
acid, benzaldehyde, hydroxyethyl acrylate, hydroxyethyl
methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,
acrylonitrile, acrylamide, N-hydroxyethyl maleimide, maleimide, and
mixtures thereof; with (b) at least one derivatizing agent selected
from the group consisting of monoalkyl ether of polyethylene
glycol, mono-alkyl ether of polypropyloxy-polyethyloxy block
copolymer, amine-containing monoalkyleneglycol, amine-containing
polyalkyleneglycol, mono-alkyl ethers of polybutyloxy-polyethyloxy
block copolymer, polyalkylene glycols containing ethylene oxide,
propylene oxide, butylene oxide or mixtures thereof, alkylene
glycol, an alkylene oxide containing 2-4 carbon atoms, amine,
polyamine, aliphatic alcohol, aromatic alcohol, aryloxy alkylene
alcohol, sulfonating agent, sulfating agent, oxidizing agent,
sugars, alkyl halide, aryl-alkylhalide, dimethyl sulfate, and
combinations thereof to form a derivatized dienophile; and (ii)
reacting the derivatized dienophile with farnesene or myrcene or
mixtures thereof by a Diels-Alder reaction.
Description
[0001] This application claims priority to, and is a continuation
of, International application No. PCT/US2013/034113 (International
Publication No. WO 2013/148842), having an International filing
date of Mar. 27, 2013. The PCT application claims priority to and
claims benefit from U.S. provisional patent application No.
61/615,949, filed Mar. 27, 2012. The entire specifications of the
PCT and provisional applications referred to above are hereby
incorporated by reference.
FIELD OF THE INVENTION
[0002] The presently described technology relates generally to
surfactants and solvents containing Diels-Alder adducts of
farnesene or myrcene, methods of derivatizing such adducts to form
surfactants and solvents, and compositions comprising or
incorporating such surfactants or solvents.
BACKGROUND OF THE INVENTION
[0003] Surfactants and solvents are used in a wide variety of
products such as household, industrial and institutional cleaning
products. Desirable attributes for such products include the
ability to emulsify, suspend or penetrate greasy or oily soils and
suspend or disperse particulates in order to clean surfaces; and
then prevent the soils, grease or particulates from redepositing on
the newly cleaned surfaces. For example, a laundry detergent
product should desirably remove dirt from clothes and then keep the
dirt in suspended solution so that it is removed with the wash
water instead of re-depositing on the washed clothes. For hard
surface cleaners, it is desirable to have the ability to wet
various surface types and couple or suspend soils to leave the
surface free from residue in the form of streaking and/or
filming.
[0004] Surfactants are also used in agricultural formulations to
emulsify, suspend, liquefy and compatibilize active ingredients and
enhance wetting to improve the delivery and efficacy of the active
ingredient.
[0005] It is highly desirable that surfactants and solvents be
biodegradable and obtained from biorenewable materials so that the
end-use products employing such surfactants or solvents are more
environmentally friendly. It is also desirable to prepare
surfactants and solvents from low-cost feedstocks that are
biorenewable and sustainable.
[0006] It has now been found that novel surfactants useful in the
formulation of a variety of end use products can be obtained from
derivatized Diels-Alder adducts of farnesene or myrcene and at
least one dienophile.
SUMMARY OF THE INVENTION
[0007] The present technology relates to surfactants prepared from
Diels-Alder adducts of farnesene or myrcene that are further
derivatized to form anionic, cationic, amine oxide, amphoteric or
nonionic surfactants.
[0008] The present technology also relates to Diels-Alder adducts
of farnesene or myrcene that are further derivatized to form useful
solvents. The present technology further relates to methods of
derivatizing the Diels-Alder adducts to form the surfactants and
solvents.
[0009] In some embodiments, the Diels-Alder adducts are prepared by
reacting farnesene or myrcene with an unsaturated carboxylic acid
or its ester or anhydride. In other embodiments, the Diels-Alder
adducts are prepared by reacting farnesene or myrcene with an
unsaturated nitrile. The Diels-Alder adducts are then derivatized
in a variety of ways to form the anionic, cationic, amine oxide,
amphoteric or nonionic surfactants. In some embodiments, the
Diels-Alder adducts are reacted with monomethyl polyethylene glycol
or monomethyl triethylene glycol to form nonionic surfactants
comprising mono- or di-esters. In other embodiments, the
Diels-Alder adducts are reacted with an amine followed by oxidation
to form amine oxide surfactants comprising amine oxides of the
Diels-Alder adducts. In further embodiments, the Diels-Alder
adducts are reacted with aromatic-substituted alcohols, followed by
hydrogenation and sulfonation to form anionic surfactants
comprising sulfonated adducts. In still further embodiments, the
Diels-Alder adducts are reacted with a sugar to form nonionic
surfactants comprising sugar esters of the adducts. In other
embodiments, the Diels-Alder adducts are hydrogenated and further
reacted with methanol and methyl or benzyl chloride,
epichlorohydrin or dimethyl sulfate to form cationic surfactants
comprising adducts containing an ammonium group. In other
embodiments, farnesene or myrcene are reacted with a previously
derivatized dienophile to form a surfactant, solvent or surfactant
precursor which may be further derivatized to form a surfactant. In
other embodiments, the Diels-Alder adducts are alkoxylated with
ethylene oxide, propylene oxide or butylene oxide to form
surfactants or solvents. In other embodiments, the Diels-Alder
adducts are reacted with a mono- or oligo-ethyleneamine, or
aminoethyl ethanolamine or mixtures thereof to form an imidazole,
followed by quaternization with a suitable quaternizing agent such
as an alkyl halide, an alkylaryl halide, epichlorohydrin or
dimethyl sulfate to form quaternium surfactants. In other
embodiments, the Diels-Alder adducts containing esters, anhydrides
or carboxylic acids are derivatized by amidation with an alkyl
amine or dialkyl amine followed by hydrogenation, followed by
oxidation to form amine oxides. In other embodiments, the
Diels-Alder adducts are hydrogenated, then sulfated, sulfonated or
phosphated. In other embodiments, the Diels Alder adducts of
farnesene or myrcene or mixtures thereof may be reacted directly
with a sulfonating agent such as, for example, sodium or potassium
bisulfite. In still further embodiments, the Diels-Alder adducts
are reacted with an aromatic substituted alcohol or an amide to
form a solvent.
BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
[0010] FIG. 1 is a graph comparing the cleaning performance of a
composition of the present technology with that of conventional
amine oxides.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The present technology provides a new approach for
incorporating biorenewable material into surfactants and solvents.
This approach comprises preparing a Diels-Alder adduct made from a
biorenewable material and further derivatizing the Diels-Alder
adduct to prepare surfactants and solvents that are useful in a
wide variety of applications.
[0012] The surfactants and solvents of the present technology are
prepared by reacting (a) biorenewable farnesene or myrcene with (b)
a dienophile to form a Diels-Alder adduct, and then derivatizing
the Diels-Alder adduct to form anionic, cationic, amine oxide,
amphoteric, or nonionic surfactants or solvents. Alternatively, the
surfactants and solvents of the present technology are prepared by
derivatizing a dienophile and then reacting the derivatized
dienophile with farnesene or myrcene to form a derivatized
Diels-Alder adduct.
[0013] The biorenewable material is selected from terpenes. A
requirement of the biorenewable material is that it functions as
the diene component in a Diels-Alder reaction. Terpenes are
composed of isoprene units and are classified according to the
number of isoprene units in the molecule. Hemiterpenes comprise a
single isoprene unit and isoprene derivatives. Isoprene or terpene
derivatives are those that have been modified chemically, such as
by oxidation or by rearrangement of the carbon skeleton.
Monoterpenes comprise two isoprene units, sesquiterpenes comprise
three isoprene units, triterpenes comprise six isoprene units and
polyterpenes comprise long chains of many isoprene units. Suitable
terpenes for use as the biorenewable material include myrcene and
farnesene. Mixtures of these terpenes are also suitable.
[0014] Farnesene refers to a group of a biorenewable sesquiterpene
chemical compounds that occur in nature and is a particularly
preferred terpene for use herein. Farnesene is found in the coating
of apples and other fruits, for example, and is thought to be
responsible for the characteristic green apple color. A commercial
source for farnesene is Amyris Inc. (Emeryville, Calif.).
[0015] The set of chemical compounds that are referred to as
farnesene include both .alpha. and .beta. isomers. The IUPAC name
for .alpha.-farnesene is 3,7,11-trimethyldodeca-1,3,6,10-tetraene,
its molecular mass is 204.36 g/mol and its molecular formula is
C.sub.15H.sub.24. The IUPAC name for .beta.-farnesene is
7,11-dimethyl-3-methylene-dodeca-1,6,10-triene. The structure of
.beta.-farnesene is represented by the following chemical formula
(I):
##STR00001##
[0016] The unsaturated carboxylic acid is selected from unsaturated
mono- and dicarboxylic acids, derivatives thereof, or mixtures
thereof that can function as dienophiles in Diels-Alder reactions.
"Derivatives" of carboxylic acids are defined herein as anhydrides,
esters, amides, imides, aldehydes, ketones and nitriles. Suitable
unsaturated carboxylic acids or derivatives for use in preparing
the Diels-Alder adducts are maleic anhydride, itaconic anhydride,
dimethyl maleate, dimethyl itaconate, maleic acid, itaconic acid,
fumaric acid, dimethyl fumarate, acrylic acid, methyl acrylate,
ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylic
acid, benzaldehyde, hydroxyethyl acrylate, hydroxyethyl
methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,
acrylonitrile, acrylamide, N-hydroxyethyl maleimide, maleimide,
vinyl alkyl ketones (where the alkyl group may be methyl, ethyl,
propyl, butyl, pentyl and hexyl), acrolein, methacrolein, and
mixtures thereof. Particularly preferred are maleic anhydride,
methyl acrylate, acrylonitrile, and itaconic anhydride.
[0017] When farnesene is reacted with maleic anhydride through a
Diels-Alder reaction mechanism, a farnesene maleate adduct may be
produced at a very fast rate (low cycle time and energy
requirement) and high yield. A synthetic scheme for the production
of a farnesene maleate adduct from a Diels-Alder reaction of
.beta.-farnesene
(.beta.-7,11-dimethyl-3-methylene-1,6,10-dodecatriene) with maleic
anhydride is shown in Diels Alder Reaction Scheme A.
##STR00002##
[0018] Representative schemes for preparing other Diels-Alder
adducts for use in preparing the surfactants and solvents of the
present technology are illustrated below. Note that in most cases,
multiple isomers of the products are possible due to the nature of
the Diels Alder reaction.
##STR00003##
##STR00004##
##STR00005##
##STR00006##
##STR00007##
##STR00008##
##STR00009##
[0019] The reaction conditions for preparing the Diels-Alder
adducts will depend upon the reactivity of the dienophile component
with the biorenewable component. In general, the reaction
temperature can vary over a wide range of temperatures of from
about -50.degree. C. to about 275.degree. C. Solvents and catalysts
can be used, if necessary, to facilitate the reaction of the
components, although it is preferred that no solvents or catalysts
be used since their removal potentially requires an additional
processing step. The components are reacted for a sufficient time
and under sufficient conditions to achieve at least a 60%
conversion of the dienophile and biorenewable components into the
Diels-Alder adduct.
Derivatizing Adducts to Prepare Surfactants
[0020] The Diels-Alder adducts prepared by reacting the
biorenewable material with the unsaturated carboxylic acid or
derivative thereof are then derivatized to form the surfactants and
solvents of the present technology. The derivatization procedures
include (1) esterification with monoalkyl polyalkylene glycols
(MPAGs) to form nonionic surfactants or solvents; (2) hydrogenation
of an aryl-containing Diels Alder adduct of farnesene or myrcene to
form a solvent, followed by sulfonation of the solvent to form an
anionic surfactant; (3) amidation and/or imidation with a
dialkylaminoalkyl amine followed by oxidation to form an amido
and/or imido dialkyl amine oxide; (4) a ring opening reaction with
one equivalent of mono-alkyl polyalkylene glycol (MPAG) followed by
neutralization of the half acid with a base to form anionic
surfactants; (5) hydrogenation of a nitrile-containing adduct,
followed by reaction with methanol and subsequent quaternization
with methyl or benzyl halide or dimethyl sulfate to form an
ammonium halide or ammonium methyl sulfate; (6) ring opening or
esterification with a sugar, optionally followed by neutralization
to form a nonionic or anionic surfactant; (7) amidation with a
mono- or di-alkyl amine to form an amide, followed by hydrogenation
or reduction to form the dialkyl amine, followed by oxidation to
form the dialkylamine oxide; (8) hydrogenation, followed by
sulfonation, sulfation or phosphation; (9) hydrogenation of a
nitrile containing adduct, followed by alkoxylation, followed by
oxidation to form an alkoxylated amine oxide; (10) reaction with a
mono- or oligo-ethyleneamine, or aminoethyl ethanolamine or
mixtures thereof to form an imidazole, followed by quaternization
with a suitable quaternizing agent such as an alkyl halide, an
alkylaryl halide, epichlorohydrin or dimethyl sulfate to form
quaternium surfactants; (11) alkoxylation with ethylene oxide,
propylene oxide, or butylene oxide to form surfactants or solvents.
In addition, (12) farnesene or myrcene may be reacted with a
previously derivatized dienophile to form a surfactant or solvent.
Finally, (13) farnesene or myrcene or mixtures thereof may be
reacted directly with a sulfonating agent such as, for example,
sodium or potassium bisulfite. Examples of several of these
derivatization procedures are described in further detail
below.
1. Esterification with MPAG
[0021] In one embodiment of the present technology, the Diels-Alder
adducts containing carboxylic acids, esters or anhydrides are
derivatized by esterifying the adducts with monoalkyl polyalkylene
glycol (MPAG) to form nonionic surfactants. The monoalkyl group in
the MPAG can have a carbon chain length of 1 to 6 carbons, and
suitable MPAGs have a molecular weight in the range of about 100 to
about 6,000, alternatively about 100 to about 4,000, preferably
about 100 to about 1500. The MPAGs may be based on ethylene oxide,
propylene oxide or butylene oxide, mixtures thereof or block
copolymers thereof. In the case of carboxylic acid or anhydride
based Diels-Alder adducts, water must be removed during the
reaction to promote ester formation. In the case of ester based
Diels-Alder adducts, alcohol must be removed during the
transesterification to promote the formation of the desired ester.
Solvents may be used to promote compatibilization of reagents
and/or provide azeotropic removal of the water of reaction.
Catalysis by acid or base may be used to promote the reaction. A
representative reaction scheme for the esterification reaction is
shown in Reaction Scheme 1:
##STR00010##
2. Hydrogenation and Sulfonation of Adducts
[0022] In another embodiment of the present technology, the
Diels-Alder adducts containing carboxylic acids, esters or
anhydrides are derivatized by esterifying the adducts with an
aromatic-substituted hydroxy alkane, followed by hydrogenation.
Suitable aromatic-substituted hydroxyl alkanes include 2-phenoxy
ethanol, benzyl alcohol, 2-phenyl ethyl alcohol, and alkoxylated
phenols having ethylene oxide and/or propylene oxide alkoxy groups.
The aromatic-substituted hydroxy alkane ester adducts may be used
"as is" in their hydrogenated or non-hydrogenated form as solvents.
Alternatively, the hydrogenated adducts can be sulfonated with a
sulfonation agent to form useful anionic surfactants. In the case
of carboxylic acid or anhydride based Diels-Alder adducts, water
must be removed during the reaction to promote ester formation. In
the case of ester based Diels-Alder adducts, alcohol must be
removed during the transesterification to promote the formation of
the desired ester. Solvents may be used to promote
compatibilization of reagents and/or provide azeotropic removal of
the water of reaction. Catalysis by acid or base is preferred to
promote the reaction. An exemplary reaction scheme for the
esterification/hydrogenation/sulfonation reaction is shown in
Reaction Scheme 2A and 2B:
##STR00011##
##STR00012##
[0023] In another embodiment of the present technology, a
dienophile containing an aldehyde and a phenyl or substituted
phenyl ring may be reacted with either farnesene or myrcene to
provide a Diels Alder adduct with useful solvent properties. This
adduct may be hydrogenated to provide a solvent. This hydrogenated
Diels Alder adduct may be sulfonated to provide products with
useful surfactant properties. An example of this embodiment is
represented in Reaction Scheme 2C.
##STR00013##
3. Amidation/Imidation Followed by Oxidation of Adducts
[0024] In another embodiment of the present technology, the
Diels-Alder adducts are derivatized by amidation and/or imidation
with a dialkyl alkylamine, followed by oxidation. Diels Alder
adducts containing carboxylic acids, esters or anhydrides may be
amidated and/or imidated with dialkylamino alkylamines.
Contemplated dialkylamino alkylamines are those having 1 to about 4
carbons in the N,N alkyl moiety and 1 to about 6 carbon atoms in
the alkylamine moiety. Suitable dialkylamino alkylamines include
N,N-dimethyl amino propyl amine, N,N-dimethyl amino ethyl amine,
N,N-diethyl amino propylamine, and N,N-dibutyl amino propyl amine.
In the case of carboxylic acids or anhydrides, water must be
removed during the reaction to promote amide/imide formation. In
the case of esters, alcohol must be removed during the
amidation/imidation to promote the formation of the desired amide
and/or imide. Solvents may be used to promote compatibilization of
reagents and/or provide azeotropic removal of the water of
reaction. Contemplated solvents include toluene, xylene and
dichlorobenzene. A large excess of dialkylamino alkylamine may be
used to promote the reaction followed by removal of the excess by
distillation. The formation of the dialkyl amino alkyl amide and/or
imide derivative is followed by an oxidation step to form the
dialkyl amine oxide derivative. Contemplated oxidizing agents are
hydrogen peroxide and peracetic acid. Representative schemes for
the amidation and/or imidation followed by oxidation reaction are
shown in reaction schemes 3A and 3B:
##STR00014##
##STR00015##
[0025] Note that depending on the conversion to imide, the final
product may be the pure imide, a mixture of imide with amide, or
the pure amide. The amine oxide derivatives described above may be
used in surfactant applications, while the amine derivatives may be
utilized in solvent applications.
4. Ring Opening/Neutralization of Adduct
[0026] In another embodiment of the present technology, the
anhydride-containing Diels-Alder adducts are derivatized by ring
opening the adduct with one equivalent of mono-alkyl ether of
polyalkylene glycol, followed by neutralization with a base. The
anhydride ring may be opened by MPAG by simply mixing equimolar
amounts of each together with exposure to mild heating (room
temperature to about 130.degree. C.). No catalyst is needed to form
the half-acid ester. MPAGs having between 1 and 30 moles of
ethylene oxide are useful for preparing these adducts. The
resulting acid is preferably neutralized to a pH between 4.5 and
8.5 using a suitable base, such as, for example sodium hydroxide,
potassium hydroxide, triethanol amine, triethyl amine, methyl
diethanol amine, sodium carbonate, and the like. The neutralization
step may occur at temperatures between 5.degree. C. and 95.degree.
C. Water may optionally be present to facilitate the neutralization
step, and may be concurrently added with the base. An example of
the ring opening/neutralization reaction is shown in Reaction
Scheme 4:
##STR00016##
[0027] These derivatives are useful as anionic surfactants.
5. Hydrogenation/Quaternization of Adduct
[0028] In another embodiment of the present technology, a
Diels-Alder adduct formed from the reaction of farnesene or myrcene
with a nitrile such as acrylonitrile or methacrylonitrile, for
example, is derivatized by hydrogenation to form an amine. The
amine is then reacted with, for example, methanol to form a
tertiary amine, followed by quaternization by reaction of the amine
with methyl chloride, benzyl chloride, or dimethyl sulfate. An
example of the reaction scheme for the hydrogenation/quaternization
reaction is shown below in Reaction Scheme 5A:
##STR00017##
[0029] An example of a process suitable for hydrogenating the
nitrile derivative to form a primary amine may be found in U.S.
Pat. No. 5,175,370. Industrially, the alkylation of primary amines
is typically conducted using alcohols, not alkyl halides, as shown
above. Alcohols are less expensive than alkyl halides and their
alkylation does not produce salts, the disposal of which is
problematic. The key to the alkylation of alcohols is the use of
catalysts that render the hydroxyl group a good leaving group. Many
industrially significant tertiary alkylamines are produced from
primary amines and alcohols such as methanol. (Karsten Eller,
Erhard Henkes, Roland Rossbacher, Hartmut Hoke "Amines, Aliphatic"
in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH,
Weinheim, 2005.) The resulting tertiary amine may then be
conveniently quaternized using a quaternizing reagent such as
methyl chloride, methyl sulfate, or benzyl chloride. The resulting
tertiary amine may also be oxidized using, for example, hydrogen
peroxide, to provide an amine oxide. The cationic surfactants may
be used in such applications as corrosion resistance compositions,
biocidal compositions, and hair conditioners, for example. The
amine oxide surfactants may be used in light duty liquid
detergents, hard surface cleaning formulations, and agricultural
adjuvant applications, for example. In a further embodiment of the
present technology, sulfobetaines may be also be prepared by
reacting amine-containing Diels Alder adduct derivatives of
farnesene, myrcene or mixtures thereof with epichlorohydrin and a
bisulfite, as shown in the example provided in Reaction Scheme 5B,
below.
##STR00018##
6. Esterification with a Sugar
[0030] In another embodiment of the present technology, the
carboxylic acid, anhydride or ester containing Diels-Alder adducts
are derivatized by esterifying the adduct with a sugar. Suitable
sugars include glycerol, sucrose, glucose, dextrose, sorbitol,
polyglycerol, fructose, lactose and sugars derived from the
chemical of enzymatic treatment of biorenewable cellulose.
Representative schemes for the esterification reaction are shown in
Reaction Schemes 6A and 6B:
##STR00019##
##STR00020##
[0031] These derivatives are expected to have useful surfactant
properties.
7. Amidation with an Alkyl Amine or Dialkyl Amine
[0032] In another embodiment of the present technology, the
Diels-Alder adducts containing esters, anhydrides or carboxylic
acids are derivatized by amidation of the adducts with an alkyl
amine or dialkyl amine. Contemplated alkyl amines or dialkyl amines
are those having 1 to about 4 carbons in the alkyl or dialkyl
moiety. Suitable alkyl or dialkyl amines include methyl amine,
ethyl amine, dimethyl amine, diethyl amine and dibutyl amine. A
reaction scheme for the amidation reaction is shown in Reaction
Scheme 7A, below. These amide derivatives can be used as solvents
and in cleaning applications.
##STR00021##
[0033] Additionally, amides from this process may be hydrogenated
and subsequently oxidized with, for example, hydrogen peroxide to
provide useful amine oxide surfactants as shown in Scheme 7B.
##STR00022##
8. Hydrogenation Followed by Sulfation or Phosphation
[0034] In another embodiment of the present technology, Diels Alder
adducts containing ketones, hydroxyls, aldehydes, carboxylic acids,
esters and anhydrides may be hydrogenated to form alcohols followed
by either sulfation or phosphation of the resulting product. The
alcohols may be optionally alkoxylated using ethylene oxide,
propylene oxide, butylene oxide or mixtures thereof prior to
sulfation. Examples of this embodiment are represented by Reaction
Schemes 8A through 8F.
##STR00023##
##STR00024##
##STR00025##
##STR00026##
[0035] The alcohols may also be reacted with cyclic sultones such
as 1,3-propane sultone, 1,4-propane sultone, or their alkyl
derivatives to provide sulfonates, as indicated by the example
shown in Reaction Scheme 8E, below.
##STR00027##
##STR00028##
9. Hydrogenation of a Nitrile Adduct, Followed by Alkoxylation,
Followed by Oxidation
[0036] In another embodiment of the present technology, a
nitrile-containing Diels Alder adduct of farnesene or myrcene may
be hydrogenated, then alkoxylated and then oxidized to form an
alkoxylated amine oxide. An example of this embodiment is
represented by Reaction Scheme 9.
##STR00029##
10. Imidazoline Formation Followed by Quaternization
[0037] In another embodiment of the present technology, an
ester-containing Diels Alder derivative of farnesene or myrcene may
be reacted with mono- or oligo-ethyleneamine, or aminoethyl
ethanolamine or mixtures thereof to form an imidazole, followed by
quaternization with a suitable quaternizing agent such as an alkyl
halide, an alkylaryl halide or dimethyl sulfate. An example of this
embodiment is represented by Reaction Scheme 10.
##STR00030##
11. Hydrogenation Followed by Alkoxylation
[0038] In another embodiment of the present technology, Diels Alder
adducts containing ketones, hydroxyls, aldehydes, carboxylic acids,
esters and anhydrides may be hydrogenated to form alcohols, which
may then be alkoxylated with ethylene oxide, propylene oxide,
butylene oxide or mixtures or block copolymers thereof to provide
nonionic surfactants and solvents. An example of this embodiment is
represented by Reaction Scheme 11.
##STR00031##
12. Diels Alder Reaction of Farnesene or Myrcene with a Derivatized
Dienophile
[0039] In another embodiment of the present technology, a
dienophile containing or derivatized using a mono-alkyl ether of
polyalkylene glycol, a mono-alkyl ether of
polypropyloxy-polyethyloxy block copolymer, an amine-containing
mono-alkylene glycol, an amine-containing polyalkylene glycol, a
mono-alkyl ether of polybutyloxy-polyethyloxy block copolymer, a
polyalkylene glycol containing ethylene oxide, propylene oxide,
butylene oxide or mixtures thereof, an alkylene glycol, an amine,
or a polyamine, or mixtures thereof may be reacted with either
farnesene or myrcene to provide a Diels Alder adduct with useful
surfactant or solvent properties or both. An example of this
embodiment is provided in Reaction Schemes 12A and 12B.
##STR00032##
##STR00033##
13. Direct Sulfonation of Farnesene
[0040] In another embodiment of the present technology, farnesene,
myrcene and mixtures thereof may be sulfonated using sodium or
potassium bisulfite (Reaction Scheme 13, below). An example
procedure for the sulfonation of alpha-olefins is provided in U.S.
Pat. No. 3,622,517.
##STR00034##
[0041] In another embodiment of the present technology, farnesene,
myrcene and mixtures thereof may be sulfonated using sulfur
dioxide, sodium sulfite and a free radical initiator such as, for
example, t-peroxy benzoate (Reaction Scheme 13B, below). An example
procedure for this route is described in R. Herke, K. Rasheed,
JAOCS, vol. 69, no. 1, (January, 1992), pg. 47-51.
##STR00035##
[0042] The surfactants and solvents of the present technology can
be used in a wide variety of applications. For example, some
applications for the surfactants and solvents of the present
technology include personal care products, such as shampoos, body
washes and liquid or solid soaps; cleaning compositions, such as
liquid hand dishwashing compositions, machine dishwashing
compositions, and hard surface cleaners; laundry detergents; fabric
softeners; agricultural compositions; and oil field and oil
recovery applications.
[0043] Compositions that include the surfactants or solvents of the
present technology will also typically include one or more
co-surfactants selected from anionic, nonionic, cationic,
ampholytic and zwitterionic surfactants or mixtures thereof.
Suitable anionic surfactants for use as a co-surfactant include
carboxylic acid salts, represented by the formula:
R.sup.1COOM
[0044] where R.sup.1 is a primary or secondary alkyl group of 4 to
30 carbon atoms and M is a solubilizing cation. The alkyl group
represented by R.sup.1 may represent a mixture of chain lengths and
may be saturated or unsaturated, although it is preferred that at
least two thirds of the R.sup.1 groups have a chain length of
between 8 and 18 carbon atoms. Non-limiting examples of suitable
alkyl group sources include the fatty acids derived from coconut
oil, tallow, tall oil and palm kernel oil. The solubilizing cation,
M, may be any cation that confers water solubility to the product,
although monovalent moieties are generally preferred. Examples of
acceptable solubilizing cations for use with the present technology
include alkali metals such as sodium and potassium, and amines such
as triethanolammonium, ammonium and morpholinium.
[0045] Primary alkyl sulfates are represented by the formula:
R.sup.2OSO.sub.3M
where R.sup.2 is a primary alkyl group of 8 to 18 carbon atoms. M
is H or a cation, e.g., an alkali metal cation (e.g. sodium,
potassium, lithium), or ammonium or substituted ammonium (e.g.
methyl-, dimethyl-, and trimethyl ammonium cations and quaternary
ammonium cations such as tetramethyl-ammonium and dimethyl
piperidinium cations and quaternary ammonium cations derived from
alkylamines such as ethylamine, diethylamine, triethylamine, and
mixtures thereof). The alkyl group R.sup.2 may have a mixture of
chain lengths. It is preferred that at least two-thirds of the
R.sup.2 alkyl groups have a chain length of 8 to 14 carbon atoms.
This will be the case if R.sup.2 is coconut alkyl, for example. The
solubilizing cation may be a range of cations which are in general
monovalent and confer water solubility, such as, for example alkali
metal cations. Other possibilities are ammonium and substituted
ammonium ions, such as trialkanolammonium or trialkylammonium.
[0046] Other suitable anionic surfactants that can be used are
alkyl ester sulfonate surfactants including linear esters of
C.sub.8-C.sub.20 carboxylic acids (i.e., fatty acids) which are
sulfonated with gaseous SO.sub.3 according to "The Journal of the
American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable
starting materials would include natural fatty substances as
derived from tallow, palm oil, etc.
[0047] Alkyl benzene sulfonates are represented by the formula:
R.sup.6ArSO.sub.3M
where R.sup.6 is an alkyl group of 8 to 18 carbon atoms, Ar is a
benzene ring (--C.sub.6H.sub.4--) and M is a solubilizing cation.
The group R.sup.6 may be a mixture of chain lengths. A mixture of
isomers is typically used, and a number of different grades, such
as "high 2-phenyl" and "low 2-phenyl" are commercially available
for use depending on formulation needs.
[0048] Paraffin sulfonates having about 8 to about 22 carbon atoms,
preferably about 12 to about 16 carbon atoms, in the alkyl moiety,
and olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to
16 carbon atoms, are also contemplated anionic surfactants for use
herein.
[0049] Sulfosuccinate esters represented by the formula:
R.sup.7OOCCH.sub.2CH(SO.sub.3.sup.-M.sup.+)COOR.sup.8
are also useful in the context of the present technology. R.sup.7
and R.sup.8 are alkyl groups with chain lengths of between 2 and 16
carbons, and may be linear or branched, saturated or
unsaturated.
[0050] Organic phosphate based anionic surfactants include organic
phosphate esters such as complex mono- or diester phosphates of
hydroxyl-terminated alkoxide condensates, or salts thereof.
Included in the organic phosphate esters are phosphate ester
derivatives of polyoxyalkylated alkylaryl phosphate esters, of
ethoxylated linear alcohols and ethoxylates of phenol. Also
included are nonionic alkoxylates having a sodium
alkylenecarboxylate moiety linked to a terminal hydroxyl group of
the nonionic through an ether bond. Counterions to the salts of all
the foregoing may be those of alkali metal, alkaline earth metal,
ammonium, alkanolammonium and alkyl ammonium types.
Nonionic Surfactants
[0051] Suitable nonionic surfactants for use as a co-surfactant in
the present compositions include alkyl polyglucosides ("APGs"),
alcohol ethoxylates, nonylphenol ethoxylates, and others.
[0052] Other suitable nonionic surfactants are poly hydroxy fatty
acid amide surfactants of the formula:
R.sup.2--C(O)--N(R.sup.1)--Z
where R.sup.1 is H, or R.sup.1 is C.sub.1-4 hydrocarbyl,
2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R.sup.2 is
C.sub.5-31 hydrocarbyl, and Z is a polyhydroxy hydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative thereof.
Preferably, R.sup.1 is methyl, R.sup.2 is a straight C.sub.11-15
alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,
and Z is derived from a reducing sugar such as glucose, fructose,
maltose, lactose, in a reductive amination reaction.
[0053] Other suitable nonionics are amine oxide surfactants. The
compositions of the present technology may comprise amine oxide in
accordance with the general formula:
R.sup.1(EO).sub.x(PO).sub.y(BO).sub.zN(O)(CH.sub.2R').sub.2.H.sub.2O
[0054] In general, it can be seen that the preceding formula
provides one long-chain moiety
R.sup.1(EO).sub.x(PO).sub.y(BO).sub.z and two short chain moieties,
--CH.sub.2R'. R' is preferably selected from hydrogen, methyl and
--CH.sub.2OH. In general R.sup.1 is a primary or branched
hydrocarbyl moiety which can be saturated or unsaturated,
preferably, R.sup.1 is a primary alkyl moiety. When x+y+z=0,
R.sup.1 is a hydrocarbyl moiety having a chain length of from about
8 to about 18. When x+y+z is different from 0, R.sup.1 may be
somewhat longer, having a chain length in the range
C.sub.12-C.sub.24. The general formula also encompasses amine
oxides where x+y+z=0, R.sup.1 is C.sub.8-C.sub.18, R' is H and
q=from 0 to 2, preferably 2. These amine oxides are illustrated by
C.sub.12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine
oxide, octadcylamine oxide and their hydrates, especially the
dihydrates as disclosed in U.S. Pat. Nos. 5,075,501 and 5,071,594,
which are incorporated herein by reference.
[0055] The presently described technology also encompasses amine
oxides where x+y+z is different from zero, specifically x+y+z is
from about 1 to about 10, and R.sup.1 is a primary alkyl group
containing about 8 to about 24 carbons, preferably from about 12 to
about 16 carbon atoms. In these embodiments y+z is preferably 0 and
x is preferably from about 1 to about 6, more preferably from about
2 to about 4; EO represents ethyleneoxy; PO represents
propyleneoxy; and BO represents butyleneoxy. Such amine oxides can
be prepared by conventional synthetic methods, e.g., by the
reaction of alkylethoxysulfates with dimethylamine followed by
oxidation of the ethoxylated amine with hydrogen peroxide.
Cationic Surfactants
[0056] Cationic surfactants suitable for use as co-surfactants
include ditallow dimethylammonium chloride (DTDMAC), fatty
alkanolamides (FAA), and quaternized diesters of trialkanolamines
and fatty acids.
[0057] Cationic detersive surfactants suitable for use in the
compositions of the present technology include those having one
long-chain hydrocarbyl group. Examples of such cationic surfactants
include the ammonium surfactants such as alkyldimethylammonium
halogenides, and those surfactants having the formula:
[R.sup.2(OR.sup.3).sub.y][R.sup.4(OR.sup.3).sub.y].sub.2R.sup.5N.sup.+X.-
sup.-
where R.sup.2 is an alkyl or alkyl benzyl group having from about 8
to about 18 carbon atoms in the alkyl chain, each R.sup.3 is
selected from the group consisting of --CH.sub.2CH.sub.2--,
--CH.sub.2CH(CH.sub.3)--, --CH.sub.2CH(CH.sub.2OH)--,
--CH.sub.2CH.sub.2CH.sub.2--, and mixtures thereof; each R.sup.4 is
selected from the group consisting of C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 hydroxyalkyl, benzyl ring structures formed by
joining the two R.sup.4 groups,
--CH.sub.2CHOH--CH(OH)C(O)R.sup.6CH(OH)CH.sub.2OH where R.sup.6 is
any hexose or hexose polymer having a molecular weight less than
about 1000, and hydrogen when y is not 0; R.sup.5 is the same as
R.sup.4 or is an alkyl chain where the total number of carbon atoms
of R.sup.2 plus R.sup.5 is not more than about 18; each y is from 0
to about 10 and the sum of the y values is from 0 to about 15; and
X is any compatible anion. The long chain cationic surfactant can
also be the quaternized version of stearamidopropyl dimethylamine
(e.g. stearamidopropyl trimethylamine chloride).
[0058] Other suitable cationic surfactants are the water-soluble
quaternary ammonium compounds having the formula:
R.sup.1R.sup.2R.sup.3R.sup.4N.sup.+X.sup.-
where R.sup.1 is C.sub.8-C.sub.16 alkyl, each of R.sup.2, R.sup.3
and R.sup.4 is independently C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
hydroxyalkyl, benzyl, or --(C.sub.2H.sub.4O).sub.x H where x has a
value from 1 to 5, and X is an anion. In an embodiment, not more
than one of R.sup.2, R.sup.3 or R.sup.4 is benzyl.
Ampholytic Surfactants
[0059] Ampholytic surfactants can be broadly described as aliphatic
derivatives of heterocyclic secondary and tertiary amines, in which
the aliphatic radical may be straight chain or branched and where
one of the aliphatic substituents contains from about 8 to about 18
carbon atoms and at least one contains an anionic
water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato
or phosphono (see U.S. Pat. No. 3,664,961, which provides specific
examples of ampholytic surfactants from col. 6, line 60, to col. 7,
line 53, incorporated here by reference). Examples of suitable
ampholytic surfactants include fatty amine oxides and fatty
amidopropylamine oxides. A specific suitable example is
cocoamidopropyl betaine (CAPB) also known as coco betaine.
Zwitterionic Surfactants
[0060] Zwitterionic synthetic detergents can be broadly described
as derivatives of aliphatic quaternary ammonium and phosphonium or
tertiary sulfonium compounds, in which the cationic atom may be
part of a heterocyclic ring, and in which the aliphatic radical may
be straight chain or branched, and where one of the aliphatic
substituents contains from about 3 to 18 carbon atoms, and at least
one aliphatic substituent contains an anionic water-solubilizing
group, e.g., carboxy, sulfo, sulfato, phosphato or phosphono. (see
U.S. Pat. No. 3,664,961, which provides specific examples of
zwitterionic surfactants from col. 7, line 65, to col. 8, line 75,
incorporated here by reference).
[0061] The compositions of the present technology also typically
include one or more adjuncts, such as, for example, builders,
enzymes, soil suspending agents, soil release and antiredeposition
agents, chelating agents, dispersing agents, stabilizers, pH
control agents, colorants, brighteners, dyes, anti-fading agents,
whiteness enhancers, color maintenance agents, color restoration
agents, dye fixatives, dye transfer agents, odor control agents,
perfumes, pro-perfumes, cyclodextrin, preservatives, anti-oxidants,
anti-corrosion agents, sanitation agents, antimicrobial agents,
disinfecting agents, pesticides, anti-abrasion agents, rinse aids,
flame retardants, water proofing agents, suds suppressors, fabric
treatment agents and UV protection agents.
EXAMPLES
[0062] The following abbreviations may be used in the present
application, especially in the following Examples:
Ammonyx LO: Lauramine oxide Ammonyx LMDO:
Lauramidopropylamine/Myristamidopropylamine oxide
CMC Critical Micelle Concentration
[0063] DiMTEG: Dimethyl triethylene glycol DMAPA: Dimethyl
amidopropyl amine MPEG-12: Monomethyl ether of polyethylene glycol
having an average of 12 moles of ethoxylation
NaLAS: Sodium Lauryl Alcohol Sulfate
[0064] MPEG: Mono-methyl ether of polyethylene glycol
[0065] The following test methods are used in the examples of the
present application.
Shake Foam Test Method
[0066] This method determines the foam height and foam stability
properties of surface active agents. A dilute surfactant solution
and castor oil, when it is used, are added to a graduated cylinder.
(It should be noted that in some experiments in the examples,
castor oil is utilized and in other experiments, it is not
utilized.) The shake foam machine inverts the cylinder for a
specified number of inversions. The foam is allowed to settle for a
brief time, and the foam height is recorded. After 5 minutes has
elapsed, the foam height is measured again.
[0067] Apparatus: [0068] 1. Shake foam machine [0069] 2. Cylinder,
graduated, 500 mL, with rubber stopper; and (3) analytical balance,
+/-0.01 g.
[0070] Reagents: [0071] 1. Tap water (however, it should be
understood by those skilled in the art that other types of water,
such as deionized water or water with higher and lower water
hardness, can also be used in the practice of the present
technology), at 25.degree. C., and [0072] 2. Castor oil.
[0073] Procedure: [0074] 1. A 0.2% active sample solution is
prepared in 25.degree. C. tap water. A 0.2% solids solution is
prepared if the active level is unknown. [0075] 2. 100.0 g+/-0.01
g, of the 0.2% sample solution is added to a 500 mL graduated
cylinder. The initial foam is kept to a minimum. [0076] 3. 2.0
g+/-0.01 g of castor oil is added to the graduated cylinder, and a
stopper is placed on the cylinder. [0077] 4. The graduated cylinder
is placed in the shake foam machine, and the clamps are secured at
the rubber stopper. [0078] 5. The shake foam machine is programmed
to invert cylinder 10 times. [0079] 6. The foam is allowed to
settle for 15 seconds. A reading of total foam height, including
the base of the 100 mL solution, is taken. [0080] 7. After 5
minutes, foam height is read and recorded again as in Step 6.
Draves Wetting Test Method
[0081] The Draves Wetting test method is based on ASTM procedure
D2281 and determines the wetting efficiency of a wetting agent. In
accordance with the test procedure, a weighted cotton test skein is
dropped into a tall cylinder containing a wetting agent having a
0.1% actives concentration dissolved in water. The time required
(in seconds) for the cotton skein to wet through and sink, relaxing
the string stirrup to which it is attached is recorded as the
sinking time. This time relates to the speed at which the wetting
agent works and can be used to compare agents.
Gardner Cleaning Test for Hard-Surface Cleaners
[0082] This test measures the ability of a cleaning product to
remove a greasy dirt soil from a white vinyl tile. The test is
automated and uses an industry standard Gardner Straight Line
Washability Apparatus. A camera and controlled lighting are used to
take a live video of the cleaning process. The machine uses a
sponge wetted with a known amount of test product. As the machine
wipes the sponge across the soiled tile, the video records the
result, from which a cleaning percentage can be determined. A total
of 10 strokes are made, and cleaning is calculated for each of
strokes 1-10 to provide a profile of the cleaning efficiency of the
product.
Example 1
Farnesene/Itaconic Anhydride Diels-Alder Adduct
[0083] Itaconic anhydride (56 g/0.50 mole) and beta-farnesene (104
g/0.51 mole) were added to a 250 mL, three-neck, round bottom flask
equipped with a heating mantle, nitrogen purge, magnetic stirring,
thermocouple and condenser. The mixture was heated to 80.degree.
C., when the appearance of the mixture changed from opalescent to
transparent and an exotherm resulted in a temperature spike to
243.degree. C. The heating mantle was removed and the stirred
mixture allowed to cool to room temperature. Gel phase permeation
chromatography indicated that the product is the Diels-Alder adduct
of farnesene and itaconic anhydride.
Example 2
Myrcene/Maleic Anhydride Diels-Alder Adduct
[0084] Maleic Anhydride (67.6 g/0.69 mole) and beta-myrcene (95.6
g/0.70 mole) were added to a 250 mL, three-neck, round bottom flask
equipped with a heating mantle, magnetic stirring, thermocouple
nitrogen purge and condenser. The mixture was heated to 50.degree.
C., when the appearance of the mixture changed from opalescent to
transparent and an exotherm resulted in a temperature spike to
about 230.degree. C. Vigorous reflux occurred. The heating mantle
was removed and the stirred mixture allowed to cool to room
temperature. Gel phase permeation chromatography indicated that the
product is the Diels-Alder adduct of myrcene and maleic
anhydride.
Example 3
Farnesene/Hydroxyethyl Acrylate Diels-Alder Adduct
TABLE-US-00001 [0085] Component Wt., g mw moles Farnesene 61.59
204.35 0.30 Hydroxyethyl acrylate 35.00 116.12 0.30 Wt. total =
96.59
[0086] Hydroxyethyl acrylate was added dropwise to beta-farnesene
over a period of about one hour at 50.degree. C. with no N2 purge.
The exotherm was minimal, so the temperature was raised over an
hour to 180.degree. C. for 6 hours to determine if the reaction
could be driven to completion by heat. The NMR is consistent with
the Diels-Alder Adduct, with HEA unsaturation peaks having
completely disappeared. Note that 4 stereoisomer possibilities
exist for the structure below.
##STR00036##
Example 4
Farnesene/Methyl Acrylate Diels-Alder Adduct
[0087] Methyl acrylate was added dropwise to beta-farnesene over a
period of about one hour at 50.degree. C. with no nitrogen purge.
It was then heated with stirring at 70.degree. C. for 3 days under
these conditions. The yield of Diels-Alder adduct after 8 hours was
59.2% based on the ratio of the product Me ester peak to the methyl
acrylate methyl peak by NMR.
[0088] The yield of Diels-Alder adduct after 3 days at 70.degree.
C. was 96.4% based on the ratio of the product Me ester peak to the
methyl acrylate methyl peak by NMR.
Example 5
Preparation of Farnesene Maleate and MPEG Half Acid Ester Salt
[0089] Farnesene (25 g, 0.122 moles/98+% purity/Bedoukian) was
mixed with maleic anhydride (MAH) (12.0 g/0.122 mole) in a 150 mL
round bottom flask equipped with nitrogen pad, magnetic stirring
and temperature control. The mixture was heated to 50.degree. C.,
whereupon the reaction mixture turned orange and the MAH pellets
dissolved. The reaction temperature rose to 202.degree. C. over the
course of approximately 1 minute, and as this exotherm was
occurring; the mixture turned nearly colorless (very pale yellow).
The reaction was cooled with an air gun to 115.degree. C. A
nitrogen bubbler was installed in place of the pad to encourage
ring closure of any diacid to the anhydride.
[0090] The temperature was then raised to 140.degree. C. and held
for 30 min., at which point MPEG (mw=298/Stepan Company/36.4
g/0.122 mole) was added and allowed to react for another hour.
Water (76.67 g/deionized) were added. The initial pH was 3.08. This
was adjusted to 7.33 using 50% NaOH, to provide a liquid product
that was pale yellow and had approximately 49% actives.
Example 6
Reaction of Farnesene Maleate with MTEG
TABLE-US-00002 [0091] Component Wt., g mw moles Farnesene maleate
99.15 302.4 0.3279 Triethylene glycol 54.91 164.2 0.3344 mono
methyl ether p-toluene sulfonic acid*H2O 0.62 190.22 0.0033
[0092] The components listed in the chart were combined along with
250 mL of toluene in a 500 mL flask equipped with a Dean-Starke
trap, condenser, heating mantle, thermocouple and magnetic
stirring. After two hours of reflux, additional triethylene glycol
mono methyl ether (MTEG, 54.91 g, 0.334 mole) was added and the
reaction mixture was refluxed to remove water of reaction for 25
hours and allowed to cool overnight to room temperature. The
toluene solution was extracted twice with 450 mL each of saturated
sodium chloride solution made slightly basic with sodium hydroxide.
The resulting toluene solution was evaporated by rotary evaporator
to yield 180.9 g of product. Over the next several days, a salt
precipitate formed in the product and settled to the bottom of the
flask. Toluene was added to the reaction mixture to reduce the
viscosity and enhance the precipitation of salt. This solution was
then vacuum filtered through Celite 545 and the toluene removed
using a rotary evaporator. The resulting product is di-(methyl
ether triethylene glycol) farnesene maleate (100% actives).
Example 7A
Reaction of Farnesene Maleate with
3-(Dimethylamino)-1-Propylamine
TABLE-US-00003 [0093] Component Wt., g mw moles Farnesene maleate
99.15 302.4 0.3279 N,N-Dimethyl amino 33.50 102.18 0.3279 propyl
amine
[0094] The reactants above were combined with 250 mL of xylene in a
500 mL flask equipped with a Dean-Starke trap, condenser, heating
mantle, thermocouple and magnetic stirring. Reflux was conducted
with subsequent removal of water between the temperatures of
129.degree. C. and 147.degree. C. for 7 hours. The resulting
product is farnesene maleimido dimethyl propylamine. Analysis
suggests that the maleimide also contains farnesene maleamide
half-acid.
Example 7B
Oxidation of Farnesene Maleimido Dimethyl Propylamine with Hydrogen
Peroxide
TABLE-US-00004 [0095] Component Wt., g mw moles Farnesene maleimide
dimethyl 110.00 386.58 0.28 propylamine Water 220.00 35% hydrogen
peroxide 28.19 34.00 0.29
[0096] The farnesene maleimide dimethyl propylamine made in Example
7A above and water, in the amounts listed in the above table, were
placed in a 500 mL flask equipped with mechanical stirrer,
condenser, addition funnel and heating mantel. The reaction mixture
was heated to 53.degree. C. followed by the addition of dry ice
until the pH reached 6.95. Hydrogen peroxide was added drop-wise
over the course of an hour with vigorous stirring until the
oxidation was complete. The temperature was raised to 70.degree. C.
with stirring for 1.5 hours to complete the oxidation. The
resulting product is DMAPA farnesene maleimide oxide. The actives
content of this surfactant in water was measured at 32% by
weight.
Example 8A
Reaction of Farnesene Maleate with MPEG 350
TABLE-US-00005 [0097] Component Wt., g mw moles Farnesene maleate
50.00 302.4 0.1653 Triethylene glycol mono methyl ether 27.15 164.2
0.1653 MPEG 350 57.87 350 0.1653 Toluene 250.00 p-toluene sulfonic
acid*H2O 0.31 190.22 0.0017
[0098] Triethylene glycol monomethyl ether was added to farnesene
maleate along with toluene and heated to 100.degree. C. for about
30 minutes in a 500 mL flask equipped with Dean-Starke trap,
condenser, thermocouple, magnetic stirring, and heating mantle to
permit ring opening and formation of the half acid ester. The
monomethyl ether of polyethylene glycol (350 mw, MPEG 350) was
added along with p-toluene sulfonic acid monohydrate and the
reagents refluxed with subsequent azeotropic water removal for 4
days. The reactants were cooled to room temperature and sodium
carbonate added with stirring for about 3 minutes, followed by
vacuum filtration through celite 545 and rotary evaporation to
remove the toluene. The resulting product is a diester of farnesene
maleate having an actives content of 100%.
Example 8B
Reaction of Farnesene Maleate with MPEG 750
TABLE-US-00006 [0099] Component Wt., g mw moles Farnesene maleate
50.00 302.4 0.1653 Triethylene glycol mono methyl ether 27.15 164.2
0.1653 MPEG 750 124.01 750 0.1653 Toluene 250.00 p-toluene sulfonic
acid*H2O 0.31 190.22 0.0017
[0100] The triethylene glycol mono methyl ether was added to
farnesene maleate along with toluene and heated to 100.degree. C.
for about 30 minutes in a 500 mL flask equipped with Dean-Starke
trap, condenser, thermocouple, magnetic stirring, and heating
mantle to permit ring opening and formation of the half acid ester.
The monomethyl ether of polyethylene glycol (750 mw, MPEG 750) was
added along with p-toluene sulfonic acid monohydrate and the
reagents refluxed with subsequent azeotropic water removal for 4
days. The reactants were cooled to room temperature and sodium
carbonate added with stirring for about 3 minutes, followed by
vacuum filtration through celite 545 and rotary evaporation to
remove the toluene. The resulting product is a diester of farnesene
maleate, having an actives content of 100%.
Example 9
Evaluation of Surfactant Properties
[0101] Compositions are prepared, each of which contains one of the
surfactants prepared in Examples 5 to 7 in water. The amount of
surfactant added to water is dictated by the test procedure
utilized to evaluate the surfactant properties. Foaming performance
of each composition is tested by the shake foam test method as
described above. Critical Micelle Concentration and Draves Wetting
properties are also measured. The same tests are conducted on a
composition containing Ammonyx LMDO in water, for comparison
purposes. Ammonyx LMDO is a standard surfactant used in laundry,
dishwash, hard surface cleaners and personal care applications to
provide foam boosting and stabilization viscosity building and
grease removal properties. The results are set forth below in Table
1.
TABLE-US-00007 TABLE 1 Example Ammonyx 7B LMDO DMAPA Lauramido
Example 5 Farnesene Propyl Example 6 Sodium Maleimide Dimethyl
DiMTEG Farnesene Amine Amine Farnesene Maleate Chemical Name Oxide
Oxide Maleate MPEG-12 Critical Micelle 17.7 88 55.4 190.4
Concentration (mg/L) Surface Tension as the 31.8 27.9 35.3 34.4 CMC
(mNm) Surface Tension at 10 42.5 45 44.2 52.2 mg/L (mNm) Shake Foam
at 15 sec. 337 307 135 212 (mL) Shake Foam at 5 min. 337 285 122
126 (mL) Shake Foam with Castor 212 162 117 196 Oil at 15 sec. (mL)
Shake Foam with Castor 212 162 115 102 Oil at 5 min. (mL) Draves
Wetting (sec.) 8.5 37 14 29
[0102] From the results, it can be seen that all of the surfactants
derived from farnesene maleate provided better wetting than the
lauramido propyl dimethyl amine oxide surfactant. Such wetting
properties are useful in applications such as agricultural
pesticide compositions to provide faster wetting which can lead to
faster kill times for the pesticides. Such wetting properties are
also useful in applications such as laundry detergent compositions
since they may provide better penetration of detergents for soil
removal. The results also demonstrate that DMAPA farnesene
maleimide oxide provides more favorable critical micelle
concentration and better foaming than lauramido propyl dimethyl
amine oxide.
Example 10
Evaluation of Surfactant Properties
[0103] Compositions are prepared that contain each of the
surfactants prepared in Examples 8A and 8B in water. Foaming
performance of each composition is tested by the shake foam test
method as described above. Critical Micelle Concentration and
Draves Wetting properties are also measured. For comparison
purposes, the same tests are conducted on a composition containing
BIOSOFT 25-7, available from Stepan Co., Northfield, Ill., in
water, and on a composition containing Makon TD-18, available from
Stepan Co., Northfield, Ill. BIOSOFT 25-7 is an ethoxylated alcohol
having a Hydrophilic Lipophilic Balance (HLB) of 12, which is
comparable to the HLB of farnesene maleate diethoxylate prepared in
Example 8A. Makon TD-18 is a tridecyl ethoxylated alcohol having an
HLB of 16, which is comparable to the HLB of farnesene maleate
diethoxylate prepared in Example 8B. The results are shown below in
Table 2.
TABLE-US-00008 TABLE 2 Example 8A Example 8B Biosoft 25-7 Farnesene
Makon TD-18 Farnesene C12-C15 Alcohol Maleate Tridecyl Alcohol
Maleate Ethoxylated with Diethoxylate Ethoxylated with Diethoxylate
Chemical Name 7 EO/HLB = 12 HLB = 12 18 EO/HLB = 16 HLB = 15
Critical Micelle 6.3 102.4 260.1 142.7 Concentration (mg/L) Surface
Tension at the 31.1 33.7 31.3 33.5 CMC (mNm) Surface Tension at 10
30.1 46 48.4 47.9 mg/L (mNm) Shake Foam at 15 sec. 255 202 300 215
(mL) Shake Foam at 5 min. 247 130 157 140 (mL) Shake Foam with
Castor 245 205 252 202 Oil at 15 sec. (mL) Shake Foam with Castor
175 115 165 127 Oil at 5 min. (mL) Draves Wetting (sec.) 12.5 1.5
48.5 16.5 Acid Value (mg KOH/g of Nm 13.1 Nm 14.6 sample) pH 5.0
4.0 5.0 4.0
[0104] From the results, it can be seen that each of the
surfactants derived from farnesene maleate has better wetting
properties than a conventional ethoxylated fatty alcohol surfactant
with comparable HLB.
Example 11
Evaluation of Cleaning Performance of DMAPA Farnesene Maleimide
Oxide
[0105] Test samples were prepared containing 300 g of a 0.2%
actives solution of the following formulations.
TABLE-US-00009 Amount D.I. Test Sample % Actives Added (g) Water
Total Example 7B DMAPA Farnesene 32.00 1.88 98.13 100.00 Maleimide
Oxide Ammonyx LO .RTM. 30.10 1.99 98.01 100.00 Ammonyx LMDO .RTM.
32.72 1.83 98.17 100.00
[0106] The test samples were evaluated for cleaning performance
using the Gardner Cleaning Test method described above. The results
are set forth below in Table 3 and shown graphically in FIG. 1.
TABLE-US-00010 TABLE 3 Average Percent Clean Stroke Number Product
1 2 3 4 5 6 7 8 9 10 DMAPA 45.36 56.33 62.42 66.36 68.12 69.43
72.39 74.63 75.00 75.60 Farnesene Maleimide Oxide Ammonyx LO 55.87
63.25 68.83 70.62 72.34 72.76 73.46 74.26 74.40 74.82 Ammonyx LMDO
52.25 60.80 63.80 68.37 70.90 72.31 73.55 73.79 74.24 75.35
Standard Deviation Among 3 Replicate Tiles Stroke Number Product 1
2 3 4 5 6 7 8 9 10 DMAPA 6.10 6.03 5.33 6.44 5.57 4.62 3.38 1.87
1.42 1.19 Farnesene Maleimide Oxide Ammonyx LO 1.20 2.32 2.06 1.76
2.69 2.52 3.27 3.89 3.96 4.29 Ammonyx LMDO 5.12 4.69 3.02 3.22 3.21
3.66 3.26 2.87 3.19 3.20
[0107] The results show that the experimental sample in accordance
with the present technology, containing the Example 7B DMAPA
farnesene maleimide oxide, gave cleaning performance comparable to
Ammonyx LMDO, which is a high performance amine oxide commercially
used for liquid dish detergents.
Example 12
Preparation of Diphenoxyethyl Farnesene Maleate 1.3 mole
Sulfonate
[0108] Farnesene maleate (126.1 g, 0.417 mole, previously prepared)
was mixed with 2-phenoxy ethanol (350 g, 2.533 moles) and heated to
140.degree. C. to ring open the anhydride. Tetra(n-butyl) titanate
(0.22 g) was added at this temperature and the reaction heated to
200.degree. C. with nitrogen purge. Butylated hydroxytoluene (0.1
g) was added to preserve the color. Upon reaching 195.degree. C.,
the heat was turned off and the reaction allowed to sit overnight
under nitrogen. The next morning, the heat was reinitiated and the
nitrogen rate turned up to provide a purge. Note that a gas
dispersion tube was used for introduction of nitrogen into the
reaction mixture within the vessel. Condensate (166 g) was
collected and discarded. Note that due to the rate of nitrogen
purge, substantial amounts of 2-phenoxylethanol were emitted as
vapor from the reaction through the condenser. The product color
was amber and transparent. The weight of the additional condensate
at this point was 16.1 g. The acid value of the product was 3.2 mg
KOH/g while the OHV was 4.4 mg KOH/g. The theoretical percentage by
weight of 2-phenoxyethanol based on this OHV is 1.08%.
[0109] Diphenoxyethyl farnesene maleate (210 g, 375 mmol) was
dissolved in ethyl acetate (400 mL) in a Parr shaker bottle and 10%
palladium on carbon (20 g) was added. The bottle was sealed,
pressurized with H2 (g) to 50 psi, and allowed to react at room
temperature for 24 hours. Periodically, aliquots were removed,
filtered through a small plug of Celite, and concentrated in vacuo.
The samples were used for proton
[0110] NMR to monitor the reaction. When complete, the mixture was
filtered through Celite, washed with ethyl acetate, and
concentrated in vacuo to dryness to give a pale yellow oil (208 g,
98%).
[0111] In a small scale batch reactor maintained at 25.degree. C.
via the circulation of thermostated water through the reactor
jacket and with a pre-established 2 L/m flow of nitrogen through
the fritted bottom of the reactor, 60.48 g (0.107 mol) of
diphenoxyethyl farnesene maleate was added to 50 mL of methylene
chloride. Over a 30 minute period, 11.21 g (0.14 mole) of sulfur
trioxide was evaporated via a 140.degree. C. flash-pot and was
bubbled through the batch reactor using the 2 L/m nitrogen stream.
The addition rate of SO3 was such that the reaction temperature
never exceeded 30.degree. C. During the addition of SO3 another 50
mL of methylene chloride was added to the reaction. At the end of
the addition, the reaction was maintained for an additional 5
minutes and was then transferred to a round bottom flask and placed
under vacuum for .about.1 hour. Titration with cyclohexylamine
showed 1.25% sulfuric acid and 85.87% sulfonic acid. The sample was
then titrated for total acid and from these results the acid was
neutralized using 89.7 g of water and 9.8 g of 50% NaOH (aq) to
give diphenoxyethyl farnesene maleate 1.3 mole sulfonate.
[0112] This anionic surfactant (10 wt. % actives) was mixed with 20
wt. % Neodol.RTM. 25-7 (C12-C15 fatty alcohol 7 mole ethoxylate)
actives, and 30 wt. % actives Steol.RTM. CS-370 (sodium laur(3)eth
sulfate) in water to provide a primary surfactant blend having a
viscosity of 6509 cps at 25.degree. C. A control prepared using 20
wt. % actives Neodol.RTM. 25-7 and 40 wt. % actives Steol.RTM.
CS-370 yielded a viscosity of 50,280 cps at 25.degree. C. These
results clearly indicate the utility of diphenoxyethyl farnesene
maleate 1.3 mole sulfonate to facilitate pourable, high
concentration laundry detergent formulations.
Example 13
Preparation of Ammonium N-Ethyl Farnesene Maleimide Sulfate
TABLE-US-00011 [0113] Component Wt.,g mw moles Farnesene 67.00
204.35 0.327869 Maleic Anhydride 32.1598 98.06 0.327869
Ethanolamine (bp = 170.degree. C.) 19.6361 61.08 0.321311
[0114] The reaction between farnesene and maleic anhydride was
conducted as previously described in Example 5, using the
quantities of farnesene and maleic anhydride shown in the table
above, in a 250 mL, round bottom flask. The reaction was allowed to
cool to room temperature. Ethanol amine was added drop-wise with
stirring, resulting in an exotherm to about 140.degree. C. Stirring
was continued, and the reaction mixture was maintained at
130.degree. C. for one hour, then nitrogen purge begun and the
mixture heated to 175.degree. C. with this purge for 6 hours. A
short section of Tygon hose was vented downward into a beaker to
collect the water and permit venting of steam, and near the end,
condensate in the adapters and necks of the flask was driven off
with a heat gun. The product provided an NMR consistent with the
pure maleimide and the reaction scheme provided below
##STR00037##
[0115] The hydroxyethyl farnesene maleimide was mixed with sulfamic
acid in the quantities indicated in the chart below in a 250 mL, 3
neck flask equipped with nitrogen purge, heating mantle, magnetic
stirring, and thermocouple temperature control. The mixture was
heated to 100.degree. C. for 17 hours.
TABLE-US-00012 Sulfation Step Components Wt., g mw moles
N-Hydroxyethyl Farnesene Maleimide 75.00 345.49 0.217083 Sulfamic
Acid 23.19 97.1 0.238791 wt. sub total = 98.19 Neutralization Step
Components Wt., g mw moles Ethanol Amine 1.33 61.08 0.021708
Methanol 118.77 32.04 0.023879
[0116] Proton NMR indicated a poor yield of sulfation, therefore,
75 mL of dimethyl formamide were added and the reaction stirred
with heating and nitrogen pad overnight at 120.degree. C. After
this step, proton NMR indicated an essentially complete conversion
to sulfate, represented by the drawing below.
##STR00038##
[0117] Ethanol amine (amt. indicated in the chart above) was then
added to this reaction product to neutralize the excess sulfamic
acid, along with 150 mL of methanol at 55.degree. C. to enhance
fluidity. Manual stirring with a spatula was initially required,
due to the taffy-like viscosity at this temperature. After 15
minutes of stirring and homogenization, the pH was 7.73. The
resulting solution was stripped of methanol via rotary evaporator
to provide ammonium N-ethyl farnesene maleimide sulfate.
[0118] The surfactant properties for this material were measured
and are provided in Table 4 below. The Draves wetting for this
surfactant at 12.5 seconds indicates potential utility in
applications such as laundry, cleaning and agricultural
adjuvants.
Example 14
Hydroxyethyl Acrylate/Farnesene Diels Alder Adduct
[0119] Hydroxyethyl acrylate was added dropwise to beta-farnesene
over a period of about one hour at 50.degree. C. with no nitrogen
pad or purge. The exotherm was minimal, so the temperature was
raised over an hour to 180.degree. C. for 6 hours. The resulting
proton NMR is consistent with the Diels Alder adduct provided in
Diels Alder Reaction Scheme E.
Example 15
Ammonium Ethyloxy Farnesene Acrylate Sulfate
[0120] Farnesene/hydroxyethyl acrylate Diels-Alder adduct (90.87
g/mw=320.47/0.284 mole/3838-29-6) was added to sulfamic acid (30.3
g/0.312 mole) whereupon the mixture was heated to 100.degree. C.
under nitrogen purge over the course of 15 hours. HNMR indicated no
loss of CH2 hydrogens adjacent to the OH. C13NMR indicated poor
conversion.
[0121] In light of the poor conversion, and the observation that a
large portion of crystalline sulfamic acid remained in the flask,
dimethyl formamide (75 mL) was added and the reaction stirred with
heating overnight at 120.degree. C. The dimethyl formamide was
removed by purging vigorously with nitrogen for 4 hours at
120.degree. C. Ethanol amine (1.71 g, 0.028 mole) was then added
along with 150 mL of methanol. The methanol was rapidly added with
stirring at 120.degree. C., and no manual stirring was required to
achieve dissolution during cooling to 55.degree. C. The pH was 7.65
at this temperature. The resulting solution was filtered through
Celite 545 and stripped of methanol via rotary evaporator to
provide ammonium ethyloxy farnesene acrylate sulfate as illustrated
by the scheme below.
##STR00039##
[0122] The surfactant properties for this material were measured
and are provided in Table 4 below. Although the CMC for this
surfactant was very high, the hydrotropic product provided
compaction performance when used at 10% actives for a 60% total
actives laundry detergent blend containing 10% actives Neodol.RTM.
25-7, 40% actives Steol.RTM. CS-370 and 10% actives ammonium
ethyloxy farnesene acrylate sulfate, yielding a flowable (viscosity
of 9239 cps) formulation at 25.degree. C. In contrast, a control
formula containing 50% actives Steol.RTM. CS-370 and 10% actives
Neodol.RTM. 25-7 provided a non-flowable formulation having a
viscosity of 50,280 cps at 25.degree. C. This clearly demonstrates
the utility of this surfactant to enable flowable, highly
concentrated laundry detergent formulations. Additionally, the
Draves wetting for this surfactant at 10 seconds indicates
potential utility in applications such as laundry, cleaning and
agricultural adjuvants.
TABLE-US-00013 TABLE 4 Ammonium Ethyloxy Ammonium N-Ethyl Farnesene
Acrylate Farnesene Maleimide Chemical Name Sulfate (Example 15)
Sulfate (Example 13) Critical Micelle Concentration (mg/L)
>10,000 1047 Surface Tension at the CMC (mNm) NA 31.9 Surface
Tension at 10 mg/L (mNm) 68.9 64.9 Shake Foam at 15 sec. (mL) 292
312 Shake Foam at 5 min. (mL) 282 295 Shake Foam with Castor Oil at
15 sec. (mL) 177 300 Shake Foam with Castor Oil at 5 min. (mL) 170
295 Draves Wetting (sec.) 10 12.5 Actives (%) 95% 95%
[0123] The present technology is now described in such full, clear,
and concise terms as to enable a person skilled in the art to which
it pertains, to practice the same. It is to be understood that the
foregoing describes preferred embodiments of the present technology
and that modifications may be made therein without departing from
the spirit or scope of the present technology as set forth in the
claims.
* * * * *